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Issue 1, 2008
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The coordination chemistry of perfluorovinyl substituted phosphine ligands, a crystallographic and spectroscopic study. Co-crystallisation of both cis- and trans-isomers of [PtCl2{PiPr2(CF[double bond, length as m-dash]CF2)}2] within the same unit cell

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Abstract

The coordination chemistry of the perfluorovinyl phosphines PEt2(CF[double bond, length as m-dash]CF2), PiPr2(CF[double bond, length as m-dash]CF2), PCy2(CF[double bond, length as m-dash]CF2) and PPh(CF[double bond, length as m-dash]CF2)2 to rhodium(I), palladium(II), and platinum(II) centres has been investigated. The electronic properties of the ligands are estimated based on ν(CO) and 1J(Rh–P) values. X-Ray diffraction data for the square-planar Pd(II) and Pt(II) perfluorovinyl-phosphine containing complexes allow estimates of the steric demand for the series of ligands PPh2(CF[double bond, length as m-dash]CF2), PEt2(CF[double bond, length as m-dash]CF2), PiPr2(CF[double bond, length as m-dash]CF2), PCy2(CF[double bond, length as m-dash]CF2) and PPh(CF[double bond, length as m-dash]CF2)2 to be determined. The (CF[double bond, length as m-dash]CF2) fragment is found to be more electron withdrawing than (C6F5) yet sterically less demanding. These ligands therefore provide a range of electron-neutral to phosphite-like electronic properties combined with a range of steric demands. This study also reveals that short intramolecular interactions from the metal centre to the β-fluorine atom cis to phosphorus of the CF[double bond, length as m-dash]CF2groups are observed in all-trans square planar complexes of the ligands. Unusually, the complex [PtCl2{PiPr2(CF[double bond, length as m-dash]CF2)}2] crystallises with both cis- and trans-isomers present in the unit cell. It appears that co-crystallisation of both isomers occurs in order to maximise fluorous regions in the crystal packing, and the extended structure displays short fluorine–fluorine contacts. The generation of mixed geometries seems to be a phenomenon of crystallisation, as solution phase NMR studies reveal the presence of only the trans-isomer.

Graphical abstract: The coordination chemistry of perfluorovinyl substituted phosphine ligands, a crystallographic and spectroscopic study. Co-crystallisation of both cis- and trans-isomers of [PtCl2{PiPr2(CF [[double bond, length as m-dash]] CF2)}2] within the same unit cell

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Publication details

The article was received on 02 Aug 2007, accepted on 19 Oct 2007 and first published on 05 Nov 2007


Article type: Paper
DOI: 10.1039/B711825B
Citation: Dalton Trans., 2008,0, 101-114
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    The coordination chemistry of perfluorovinyl substituted phosphine ligands, a crystallographic and spectroscopic study. Co-crystallisation of both cis- and trans-isomers of [PtCl2{PiPr2(CF[double bond, length as m-dash]CF2)}2] within the same unit cell

    N. A. Barnes, A. K. Brisdon, F. R. W. Brown, W. I. Cross, C. J. Herbert, R. G. Pritchard and G. Sadiq, Dalton Trans., 2008, 0, 101
    DOI: 10.1039/B711825B

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